CN1194891C - Composite molecular sieve and preparing process thereof - Google Patents
Composite molecular sieve and preparing process thereof Download PDFInfo
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- CN1194891C CN1194891C CNB021004528A CN02100452A CN1194891C CN 1194891 C CN1194891 C CN 1194891C CN B021004528 A CNB021004528 A CN B021004528A CN 02100452 A CN02100452 A CN 02100452A CN 1194891 C CN1194891 C CN 1194891C
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Abstract
The present invention relates to a composite molecular sieve and a preparation method thereof, wherein the composite molecular sieve can be used for the field of catalytic cracking, catalytic pyrolysis, hydrocracking, fine chemical industry, etc. Faujasite which is prepared by a guide agent method is used for preparing reaction mixture gel of a first micropore molecular sieve, the crystallization of the first phase lasts for 8 to 48 hours at the temperature of 80 to 130 DEG C, mould plate agents or crystal seeds used for synthesizing the other micropore molecular sieve are added, the acidity and the alkalinity of the reaction mixture are adjusted, the heating-up crystallization of mixture lasts for 2 to 96 hours at the temperature of 120 to 240 DEG C, and the composite molecular sieve is obtained. The molecular sieve composition contains two or more than two kinds of molecular sieves, quality of gasoline obtained from the composite molecular sieve is obviously improved, the octane number and the isoparaffin content of the gasoline are increased, the olefinic content is obviously lowered, and the utilization ratio of silicon aluminum sources during the synthesis of the faujasite is improved.
Description
Technical field
The present invention can be used for catalytic cracking, and fields such as catalytic pyrolysis, hydrocracking and fine chemistry industry specifically, are a kind of composite molecular sieves and preparation method thereof.
Background technology
Since the sixties in 20th century, the faujusite of various modifications, for example the main active component of conducts such as REY, REHY, USY, REUSY is widely used in catalytic cracking, in the hydrocarbon conversion reactions such as hydrocracking.In order to adapt to the more and more stricter environmental protection requirement and the ability of adaptation to market variations, many zeolite molecular sieves constituent element catalyzer is used for catalytic cracking, hydrocarbon reaction processes such as hydrocracking.At the beginning of the eighties, the ZSM-5 zeolite is used for catalytic cracking process as the catalytic cracking octane enhancing additive.In recent years, some high-silica zeolites such as L zeolite, β zeolite, SAPO, VPI-5 molecular sieve, and some mesoporous molecular sieves such as MCM-41 and MSU etc. are useful on the report of oil-refining chemical technologies such as catalytic cracking.
The division of said here micropore, mesopore and macropore is to stipulate according to international material association: the material aperture is a poromerics (Microporous) less than 2nm's; The aperture is at the genus mesopore of 2-50nm or be mesoporous material (Mesoporous); Greater than 50nm is large pore material (Macroporous).
At present, many zeolite molecular sieves constituent element Preparation of catalysts prior art generally has two kinds of methods: the one, and earlier that their machinery is mixed after the modification of various molecular sieves difference, make catalyzer then; Another kind method is that various molecular sieves are made catalyzer respectively, and use mixed then back.
What more than adopt is various molecular sieve to be carried out machinery mix and prepare catalyzer.Based on understanding, two or more is had the different tart molecular sieves of difference or same structure combine (as among crystal grain or sieve particle) the oil-refining chemical detailed process; Perhaps the zeolite molecular sieve that will have identical topological framework makes up, and the mode by symbiosis or eutectic obtains bimolecular sieve material; Also the molecular sieve with different structure can be made up, obtaining corresponding bimolecular sieve nest is, bring into play the synergy between them, different being reflected in a certain zone (among a sieve particle) carried out, restrain some disadvantageous reaction, optimize the product result, heat transfer that will help reacting and mass transfer like this, this will be mixed more favourable than machinery.As core-shell type molecular sieve, promptly have the outside that a kind of molecular sieve (shell) is enclosed in another kind of molecular sieve (nuclear) and form a kind of new molecular screen material.The catalysis behavior of stratum nucleare molecular sieve is subjected to the influence of shape selectivity, activity, selectivity and the diffusion control of shell molecular sieve.
U.S. Pat 4,847,224, US 4,946, and 580 disclose to join by the nucleation gel that will contain zeolite A crystal seed and have helped in the fresh gel of zeolite B synthetic, and crystallization under the synthesis condition of zeolite B obtains containing the product of two kinds of zeolites of AB.Zeolite A, B have identical structural unit, and zeolite B is enclosed in the outside of zeolite A, have the effect of chemical bond between the two, and mechanical property also is improved.A comprises saspachite and omega zeolite, and B comprises omega zeolite and mordenite.They are used for the catalytic cracking result and show that yield of gasoline increases, and coke yield descends.
U.S. Pat 4,503,164 disclose synthetic a kind of method with molecular sieve of hud typed structure, and its kernel is the borosilicate crystal, and shell is a silica crystals, and two kinds of crystal have identical structure.The preparation method is in the gel that will join synthetic shell molecular sieve as the molecular sieve of kernel, and crystallization forms the core-shell type zeolite catalyzer then.
Propose carrier (α-Al among the world patent WO98-06495
2O
3) through after the template solution pre-treatment, mixed with the gel of synthesis of molecular sieve again, crystallization under rotation or static conditions forms molecular sieve crystal in the hole of carrier He outside the hole, obtain composite catalyst.The effect of template is the formation of inducing molecule sieve, makes that the surface energy at carrier forms molecular sieve.
U.S. Pat 5,888,921 have proposed a kind of synthetic multi-layer structure, and each layer has the hud typed bimolecular sieve of different structures, acidity and composition.Molecular sieve as kernel is an aluminosilicate molecular sieves, comprises that faujusite, Y, L, A, mordenite equal aperture are the zeolite of 5～7 , and the molecular sieve that is used for shell is phosphate aluminium molecular sieve (ALPO
4, SAPO, MeAPO, MeAPSO's is a kind of).The mentality of designing of this bimolecular sieve is: shell acidity is weak (as ALPO-5), and kernel acidity is strong (ZSM-5).It uses as additive, and molecule bigger in the product of y-type zeolite is a little less than cracking on the shell ALPO-5, and isomerization is strong.But littler molecular energy enters kernel and the short chain isomerization takes place on strong acidic site.Its synthetic method is for to join the zeolite molecular sieve powder in the slurries of phosphoric acid, aluminium source, metal-salt and organic amine, stir 1-12h under the room temperature, put in the autoclave of inner liner polytetrafluoroethylene, 130-240 ℃ is reacted 12-18h down in baking oven, washing then, dry, roasting (530-570 ℃, N
2Protection roasting 5-15h, roasting 1-3h in air then) obtain this bimolecular sieve catalyst.
U.S. Pat 5,972,205 with US 5,888, and 921 synthetic bimoleculars sieve is used for fluid catalytic cracking (FCC) as additive, it and ZSM-5 specific energy raising C mutually
4, C
5The productive rate of alkene, and the gasoline yield loss is little.This bimolecular sieve is different with the mechanical mixture of these two kinds of molecular sieves, shows structure and catalytic cracking in nature.
World patent WO 96-01687 has provided a kind of preparation method of compound molecule sieve membrane, the matrix that scribbles mesoporous molecular sieve or oxide skin is put in the reactor, the gel that adds molecular sieve then, reaction at a certain temperature makes certain thickness molecular screen membrane.The preparation method of molecular screen membrane is similar substantially to the method for preparing core-shell type molecular sieve, and key is that this molecular sieve is easy to crystallization on matrix.
In above-mentioned patent, research be to form bimolecular sieve material between the micro-pore zeolite molecular sieve.In recent years, the achievement in research of mesoporous molecular sieve makes it possible to mesopore, micro porous molecular sieve are made up, mesoporous-microporous composite molecular sieve material in obtaining.
The investigator of Fudan University has synthesized mesoporous-microporous composite molecular sieve among two kinds of β/MCM-41, the ZSM-5/MCM-41 (the open CN1208718 of Chinese patent, 1999; J.Phys.Chem.B, 2000,104,2817-2823; SCI, 1999,20 (3), 356-358).They adopt two directed agents methods by two step crystallization, and earlier synthetic MCM-41 mesoporous molecular sieve forms micro porous molecular sieve with the unbodied crystallization of pore wall of mesoporous molecular sieve again, thinks that crystallization of pore wall is to follow solid transformation mechanism.The synthetic composite molecular screen is better than the middle micro porous molecular sieve of mechanically mixing in acidic catalyst like this, wherein the cracking activity of the n-dodecane of sample S2 is compared with ZSM-5 mechanically mixing sample with MCM-41 and is improved 9 percentage points of (J.Phys.Chem.B, 2000,104,2817-2823).
Karlsson is with C
6H
13(CH
3)
3NBr and C
14H
29(CH
3)
3NBr is that template changes temperature of reaction, regulates template concentration, and synthetic MFI/MCM-41 type matrix material (Microporous MesoporousMater., 1999,27,181-192.).
Introduced a kind of synthetic method of middle mesoporous-microporous composite molecular sieve in the Chinese patent application that the investigator submits 01119908.3 of Petroleum Univ., be to prepare synthetic microporous molecular sieve earlier (as Y zeolite with the method for routine, ZSM-5, beta-molecular sieve) reaction mixture gel, and then carry out the crystallization of fs under certain condition, behind the crystallization certain hour, adjust the potential of hydrogen of reaction mixture, and the synthetic used template of mesoporous molecular sieve of adding, the silicon source and/or the aluminium source that also can add needs in case of necessity again, also can add the allied compound that contains other transition metal so that introduce the heteroatoms metal, also can add relevant auxiliary agent again, then, under certain temperature and pressure, carry out the hydrothermal crystallizing of subordinate phase again, behind the crystallization certain hour, obtain the said middle mesoporous-microporous composite molecular sieve composition of the present invention.
Adopt the method for preparing binder free zeolite (as the zeolite bound zeolite), also can prepare a series of composite molecular sieve materials.
Exxon Chemical Patents Inc. has applied for a series of patents, comprises WO 96-16004, WO97-45384, and US 5,460,796, and US 5,665,325, and US 5,933, patents such as 642.In these patents, by crystallization in a certain proportion of sodium hydroxide and template solution bondd the molecular sieve extrudate of silicon-dioxide or the silica binder in the spraying granule, prepared zeolite bound zeolite molecular sieve (Zeolite Bound Zeolite), second kind of zeolite symbiosis on first kind of zeolite, some or all of covering on first kind of zeolite, form hud typed structure, can regulate inside and outside different acidity so as required.Reduce surface acidity and can reduce the by product that the non-selective catalysis because of the surface causes.The condition of synthetic this binder free zeolite is that first kind and second kind of zeolite are zeolites of the same type, and perhaps they will mate on crystalline structure.It has better intensity and integrity, has overcome the shortcoming of amorphous binding agent.Can be used for hydrocarbon conversion reactions, comprise that the cracking of petroleum naphtha, the isomerization of alkylaromatic hydrocarbon, the disproportionation of toluene, transalkylation and alkylation, the naphtha reforming of aromatic hydrocarbons are that aromatic hydrocarbons, alkane or conversion of olefines are the oxidation conversion of aromatic hydrocarbons and hydrocarbon product.U.S. Pat 5,933 discloses in 642 and has been MFI type zeolite inside and outside synthetic, and the kernel silica alumina ratio is 80: 1, and shell is 900: 1, and its selectivity and resistive connection charcoal ability all are improved in disproportionation reaction.WO 99-28032, US 6,150, by add silicalite as crystal seed in preparation silica-bonded zeolite process, synthesize the ZSM-5 bound zeolite in 293, have the crystalline structure different with ZSM-5 as the zeolite of kernel, are TON type zeolite.Prepared among the WO 98-54092 with FAU and EMT is the zeolite bonding FAU type zeolite of zeolite binding agent.In the sodium hydroxide solution of crystallization zeolite binding agent, add crown ether, can reduce or eliminate fully the generation of P type zeolite.
Prepared the zeolite bound zeolite that contains hydrogenation metal platinum among the world patent WO97-45197, the patent of the preparation of its zeolite bound zeolite and Exxon company is similar, just adds the solution of platinum when preparation silica-bonded zeolite.Make the distribution of platinum than other method homogeneous more like this.
The discharging of residue silicon-dioxide in the mother liquor improves the utilization ratio in silicon source when reducing synthesis zeolite, has proposed in the document to utilize mother liquor to come synthesis zeolite.Here said mother liquor is meant the last liquid of elimination molecular sieve behind the hydrothermal crystallizing.
German patent DE 2,853 in 986 patents, adds acid aluminium salt and forms SiO in the NaY mother liquor
2-Al
2O
3-H
2O gel, filtered and recycled are used for the synthetic of NaY zeolite, have reduced the loss in silicon source, and waste water has also reached emission standard.The author has also carried out studying (Liu, Conghua in the document below; Gao, Xionghou; Ma, Yanqing; Pan, Zhongliang; Tang, Rongrong (PetrochemicalResearch Institute of Lanzhou Oil Refinery, Lanzhou 730060, Peop.Rep.China), Study on the mechanism of zeolite Y formation in the processof liquor recycling, Microporous Mesoporous Mater., 25 (1-3), 1-6 (English) 1998).
US 4,144, in 194 with mother liquor CO
2Handle the formation gel and, add alum solution and 23%NH again with sodium aluminate 29.5 ℃ of ageings
4OH, the filter cake of adding NaY zeolite, then with this mixture agitation and filtration, filter cake is cleaned back (NH
4)
2SO
4Exchange gets catalyzer with re chloride exchange system again.
Lipkind B.A., people such as V.A.Burylov utilize Na
2O-Al
2O
3-SiO
2-H
2The mother liquor of O system synthetic zeolite synthesizes NaA, faujusite, mordenite and chabazite etc., can utilize mother liquor (Lipkind fully, B.A., V.A.Burylov, et al., Waste-free manufacture ofzeolites, Khim.Tekhnol.Topl.Masel, (2), 53-6 (Russian) 1980).
The mother liquor of the synthetic heteroatoms ZSM-5 molecular sieve of utilization utilizes organic amine wherein as the raw material of synthetic ZSM-5 among the CN1230466, and the expense of minimizing template and organic amine are to the pollution of environment.
Be the synthetic ZSM-5 molecular sieve of raw material with the NaY mother liquor among the CN 1057067C.At first with the acid deposition of NaY mother liquor, the spray-dried silicon aluminium microsphere of making mixes this silicon aluminium microsphere and NaOH, water and molecular sieve crystal seed again, and making mol ratio is SiO
2/ Al
2O
3=20～80, OH
-/ SiO
2=0.05～0.3, H
2O/SiO
2=2～10 reaction mixture is used the ordinary method hydrothermal crystallizing, thereby effectively utilizes the NaY mother liquor, has reduced the synthetic cost of ZSM-5 molecular sieve, has improved the combined coefficient of single still unit volume.
US 5,637, utilize the mother liquor (filtered solution) of synthesizing high-silicon faujusite ECR-4, ECR-32, ECR-30, ECR-35 in 287, add necessary silicon source, aluminium source and template, synthesized above-mentioned zeolite.Be characterized in making full use of template and the silicon source in the mother liquor, directly utilized mother liquor, rather than reclaimed the silicon-dioxide in the mother liquor, greatly reduced the usage quantity of expensive template; Eliminated the stray crystal that forms when utilizing mother liquor synthetic.
In publication of publishing and patent documentation, do not find to adopt the method for fractional crystallization, utilize the technology that contains the synthetic microporous combined molecular sieve of zeolite mixed solution of synthetic faujasites.
Technology contents
The objective of the invention is to provide the synthetic method of the combined molecular sieve of a kind of micropore, in the gained molecular sieve, contain the micro porous molecular sieve composition of two or more different structure, meanwhile, the utilization ratio of silicon and aluminum source when improving synthetic faujasites.
The reaction mixture gel for preparing the synthetic first kind of micro porous molecular sieve of faujusite preparation with directing agent method, then 80～130 ℃ of following crystallization 8～48 hours, carry out the fs crystallization, first crystallization is after the stage, the template or the crystal seed that add synthetic another kind of micro porous molecular sieve, and the potential of hydrogen of adjustment reaction mixture, carry out the hydrothermal crystallizing of subordinate phase then, the second crystallization rank were 120～240 ℃ of following intensification crystallization 2～96 hours, second crystallization stage acidity-basicity ph=9.0～12.0 obtain said combined molecular sieve.
The present invention also adopts following technical scheme:
Carry out crystallization under the condition of first kind of molecular sieve of first crystallization stage employing, product directly adds the template or the crystal seed reagent of synthetic another kind of molecular sieve in same synthesis reactor afterwards, carries out the crystallization of subordinate phase again.
Synthetic second kind of template or crystal seed that molecular sieve is used before the fs crystallization, or adds in crystallization process.
Regulate potential of hydrogen sulfuric acid, hydrochloric acid, phosphoric acid or acetate.
Said template is: ethanol, Virahol, with the primary amine of ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, with the secondary amine of dipropylamine, dibutylamine or with the quaternary ammonium salt of tetraethylammonium bromide, 4-propyl bromide, Tetrabutyl amonium bromide and composition thereof or their alkaline hydrated oxide.
Said crystal seed is the powder of second kind of molecular sieve.
The molecular sieve that contains two or more in prepared combination of molecular sieve, the molecular sieve in the composite molecular sieve is a micro porous molecular sieve.
Said first kind of molecular sieve is Y and X type molecular sieve.
Second kind of molecular sieve is ZSM-5, ZSM-4, ZSM-11 and beta-molecular sieve.
Its silica alumina ratio or be 30,50,500, or pure silicon ZSM-5.
The silicon and aluminum source of synthetic second kind of molecular sieve comes from the reaction mixture of first kind of molecular sieve fully, or adds silicon and aluminum source.
Said aluminium source is a Tai-Ace S 150, sodium aluminate, aluminium hydroxide, pseudo-boehmite.
Said silicon source is: water glass, silicon sol, silica gel, white carbon black.
The resulting combined molecular sieve of the present invention can be used for various hydrocarbon conversion processes, as catalytic cracking, hydrocracking etc.For example, in the laboratory this composite molecular sieve being carried out ammonium and rare earth exchanged, behind the super stabilizing, is matrix with kaolin, and aluminium colloidal sol is that adhesive preparation obtains catalyzer.Catalytic cracking reaction evaluation to wax oil shows that the resulting quality of gasoline of this composite molecular sieve obviously improves, and the octane value and the isoparaffin content of gasoline are improved, and olefin(e) centent obviously reduces.
The present invention relates to the synthetic of different structure, tart composite molecular sieve, when being synthetic faujasites, behind the hydrothermal crystallizing certain hour, adjust the potential of hydrogen of mixed solution (solidliquid mixture) in the synthesis reactor, add or do not add silicon and aluminum source, adopt the method for fractional crystallization to synthesize this combined molecular screen material
Description of drawings
The XRD figure of Fig. 1 embodiment three;
Fig. 2 embodiment Three S's EM schemes (amplifying 5000 times);
The XRD figure of Fig. 3 embodiment four
Embodiment
The following examples will the present invention is further illustrated.
X-ray diffraction (XRD) analysis is adopted the BDX-3200 type X-ray powder diffraction instrument of company of Qingniao Co. of Peking University, and degree of crystallinity and standard model carry out strength ratio and obtain.Scanning electron microscope (SEM) adopts Cambridge S-360 type instrument to finish.
Embodiment one
U.S. Pat 3,639,009 and US3 are adopted in the preparation of directed agents, the method preparation for preparing the NaY directed agents that is proposed in 671,191.
17.30 gram water glass with deionized water 13.46 gram dilutions, are under agitation added 50w% 18 water aluminum sulfate hydrate solution 1.31 grams then successively, directed agents 4.03 grams, low alkali sodium aluminate (chemical pure, Al
2O
3Be 54w%, Na
2O is 41w%, Beijing state China new chemical materials company) solution (Al
2O
3Be 16.2w%, Na
2O is 12.3w%) 5.25 grams and 3.77 sulphuric acid solns that restrain 3 mol are made into gel, stir the reactor of after 30 minutes gel being put into 100 milliliters of inner liner polytetrafluoroethylenes in 100 ℃ of crystallization 24 hours, after the cooling, add tetraethylammonium bromide 0.68 gram and 4-propyl bromide (analytical pure, commercially available) 1.06 grams, stirred 10 minutes, use the sulfuric acid (analytical pure of 3 mol then, the Beijing Chemical Plant produces) solution 6.25 grams transfer mixed serum pH values, stir on 30 minutes bonnets reactor in 180 ℃ of crystallization 18 hours.After reaction finishes, product after filtration, washing, drying, identify to have ZSM-5 characteristic peak and NaY characteristic peak through XRD, a small amount of P type stray crystal is arranged.
Embodiment two
The preparation of NaY directed agents is with embodiment one.
17.30 gram water glass with deionized water 13.46 gram dilutions, are under agitation added 50w% 18 water aluminum sulfate hydrate solution 1.31 grams then successively, directed agents 3.89 grams, low alkali sodium aluminate (solution (Al
2O
3Be 16.2w%, Na
2O is 12.3w%) 5.25 grams and 3.77 sulphuric acid solns that restrain 3 mol are made into gel, stir the reactor of after 30 minutes gel being put into 100 milliliters of inner liner polytetrafluoroethylenes in 100 ℃ of crystallization 24 hours, after the cooling, add tetraethylammonium bromide 0.68 gram and 4-propyl bromide 1.06 grams, stirred 10 minutes, transfer mixed serum pH values with sulphuric acid soln 6.20 gram of 3 mol then, stir on 30 minutes bonnets reactor in 140 ℃ of crystallization 40 hours.After reaction finishes, product after filtration, washing, drying, identify to have ZSM-5 characteristic peak and NaY characteristic peak, no P type stray crystal through XRD.
Embodiment three
The preparation of NaY directed agents is with embodiment one.
17.30 gram water glass with deionized water 13.46 gram dilutions, are under agitation added 50w% 18 water aluminum sulfate hydrate solution 1.31 grams then successively, directed agents 4.03 grams, low alkali aluminium acid sodium solution (Al
2O
3Be 16.2w%, Na
2O is 12.3w%) 5.25 grams and 3.77 sulphuric acid solns that restrain 3 mol are made into gel, stir the reactor of after 30 minutes gel being put into 100 milliliters of inner liner polytetrafluoroethylenes in 100 ℃ of crystallization 24 hours, after the cooling, add dehydrated alcohol (analytical pure, Beijing northization fine chemicals limited liability company) 0.25 gram, stirred 10 minutes, and transferred mixed serum pH values with sulphuric acid soln 6.25 gram of 3 mol then, stir on 30 minutes bonnets reactor in 160 ℃ of crystallization 24 hours.After reaction finishes, product after filtration, washing, drying, identify to have ZSM-5 characteristic peak and NaY characteristic peak through XRD.
XRD determining result shows that its crystallinity Y and ZSM-5 are respectively 50.4% and 15.6%.XRD spectra as shown in Figure 1, SEM schemes shown in Fig. 2 (amplifying 5000 times).
Embodiment four
The preparation of NaY directed agents is with embodiment one.
17.30 gram water glass with deionized water 13.46 gram dilutions, are under agitation added 50w% 18 water aluminum sulfate hydrate solution 1.31 grams then successively, directed agents 4.03 grams, low alkali aluminium acid sodium solution (Al
2O
3Be 16.2w%, Na
2O is 12.3w%) 5.25 grams and 3.77 sulphuric acid solns that restrain 3 mol are made into gel, stir the reactor of after 30 minutes gel being put into 100 milliliters of inner liner polytetrafluoroethylenes in 100 ℃ of crystallization 24 hours, after the cooling, add tetraethylammonium bromide 0.68 gram and 4-propyl bromide 1.06 grams, stirred 20 minutes, use sulfuric acid (analytical pure, Beijing Chemical Plant produce) solution 6.25 grams of 3 mol to transfer mixed serum pH values then, stir on 30 minutes bonnets reactor in 160 ℃ of crystallization 24 hours.After reaction finishes, product after filtration, washing, drying, identify to have ZSM-5 characteristic peak and NaY characteristic peak through XRD, XRD determining result shows that its crystallinity Y and ZSM-5 are respectively 59.5% and 22.1%.XRD spectra as shown in Figure 3.
Embodiment five
The preparation of NaY gel is with embodiment one, and difference is, changing added template into silica alumina ratio is 500 ZSM-5 zeolite seed crystal, regulates after the potential of hydrogen in 160 ℃ of crystallization 24 hours.After reaction finishes, product after filtration, washing, drying, identify to have ZSM-5 characteristic peak and NaY characteristic peak through XRD.
Embodiment six
The preparation of NaY gel is with embodiment one.
Behind the NaY100 ℃ of crystallization 10h, stop crystallization, be cooled to room temperature.Add tetraethylammonium bromide 0.67 gram and 4-propyl bromide 1.02 grams then, stirred 20 minutes, cover reactor and continue at 100 ℃ of crystallization 14h.After being cooled to room temperature, transfer mixed serum pH values, stir on 20 minutes bonnets reactor in 160 ℃ of crystallization 24 hours with the sulfuric acid of 3 mol (analytical pure, the Beijing Chemical Plant produces) solution 6.20 grams.After reaction finishes, product after filtration, washing, drying, identify to have ZSM-5 characteristic peak and NaY characteristic peak through XRD.
Embodiment seven
The preparation of NaY gel is with embodiment one.
Behind the NaY100 ℃ of crystallization 24h, stop crystallization, be cooled to room temperature.Add to add tetraethylammonium bromide 0.67 gram and 4-propyl bromide 1.02 grams then, stirred 20 minutes, use the phosphoric acid solution accent mixed serum pH value to 10.08 of 40wt%, stir on 20 minutes bonnets reactor in 160 ℃ of crystallization 24 hours.After reaction finishes, product after filtration, washing, drying, identify to have ZSM-5 characteristic peak and NaY characteristic peak through XRD.
Claims (13)
1. the preparation method of a combined molecular sieve, be characterized in: the reaction mixture gel for preparing the synthetic first kind of micro porous molecular sieve of faujusite preparation with directing agent method, then 80～130 ℃ of following crystallization 8～48 hours, carry out the fs crystallization, first crystallization is after the stage, the template or the crystal seed that add synthetic another kind of micro porous molecular sieve, and the potential of hydrogen of adjustment reaction mixture, carry out the hydrothermal crystallizing of subordinate phase then, the second crystallization rank were 120～240 ℃ of following intensification crystallization 2～96 hours, second crystallization stage acidity-basicity ph=9.0～12.0 obtain said combined molecular sieve.
2. according to the preparation method of the described a kind of combined molecular sieve of claim 1, be characterized in: carry out crystallization under the condition of first kind of molecular sieve of first crystallization stage employing, product directly adds the template or the crystal seed reagent of synthetic another kind of molecular sieve in same synthesis reactor afterwards, carries out the crystallization of subordinate phase again.
3. according to the preparation method of the described a kind of combined molecular sieve of claim 1, be characterized in: synthetic second kind of template or crystal seed that molecular sieve is used before the fs crystallization, or adds in crystallization process.
4. the preparation method of a kind of combined molecular sieve according to claim 4 is characterized in: regulate potential of hydrogen sulfuric acid, hydrochloric acid, phosphoric acid or acetate.
5. the preparation method of a kind of combined molecular sieve according to claim 1, be characterized in: said template is: ethanol, Virahol, with the primary amine of ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, with the secondary amine of dipropylamine, dibutylamine or with the quaternary ammonium salt of tetraethylammonium bromide, 4-propyl bromide, Tetrabutyl amonium bromide and composition thereof or their alkaline hydrated oxide.
6. the preparation method of a kind of combined molecular sieve according to claim 1, be characterized in: said crystal seed is the powder of second kind of molecular sieve.
7. combined molecular sieve is characterized in that containing two or more molecular sieve in prepared combination of molecular sieve, the molecular sieve in the composite molecular sieve is a micro porous molecular sieve.
8. a kind of combined molecular sieve according to claim 8 is characterized in that said first kind of molecular sieve is Y and X type molecular sieve.
10. a kind of combined molecular sieve according to claim 8 is characterized in that second kind of molecular sieve is ZSM-5, ZSM-4, ZSM-11 and beta-molecular sieve.
11. a kind of combined molecular sieve according to claim 10 is characterized in that its silica alumina ratio or is 30,50,500, or pure silicon ZSM-5.
12. a kind of combined molecular sieve according to claim 8 is characterized in that the silicon and aluminum source of synthetic second kind of molecular sieve comes from the reaction mixture of first kind of molecular sieve fully, or adds silicon and aluminum source.
13. a kind of combined molecular sieve according to claim 12 is characterized in that said aluminium source is Tai-Ace S 150, sodium aluminate, aluminium hydroxide or pseudo-boehmite.
14. a kind of combined molecular sieve according to claim 8 is characterized in that said silicon source is: water glass, silicon sol, silica gel or white carbon black.
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| CN101279285B (en) * | 2007-04-04 | 2010-05-19 | 中国石油化工股份有限公司 | Naphtha catalytic pyrolysis catalyst for preparing ethylene propylene |
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-
2002
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100450617C (en) * | 2005-10-18 | 2009-01-14 | 中国石油天然气股份有限公司 | A kaolin based compound molecule sieve and preparation method thereof |
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